CN107313292A - A kind of wrapping paper Cypres and preparation method thereof - Google Patents
A kind of wrapping paper Cypres and preparation method thereof Download PDFInfo
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- CN107313292A CN107313292A CN201610277785.6A CN201610277785A CN107313292A CN 107313292 A CN107313292 A CN 107313292A CN 201610277785 A CN201610277785 A CN 201610277785A CN 107313292 A CN107313292 A CN 107313292A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention discloses a kind of wrapping paper Cypres and preparation method thereof.The Cypres of the present invention, it is made up of following each component：Natural polymer, natural macromolecule modification agent, unsaturated hard monomer, unsaturated soft monomer, modified petroleum resin, cationic monomer, function monomer, initiator I, initiator II, deionized water；C 9 petroleum resin is modified by the present invention using maleic anhydride, obtains the modification C 9 petroleum resin containing anhydride group in molecule；Using peroxide as initiator, the progress copolymerization of the modification C 9 petroleum resin of preparation, unsaturated monomer, cationic monomer and natural polymer is prepared into Cypres.The sizing efficiency that Cypres prepared by the present invention have had under the applying glue environment of low resin added or rather harsh, also has the advantages that curing is fast, cost performance is high, humidity resistance is good, safety and environmental protection.
Description
Technical field
The present invention relates to sheet surface treating agent technical field, particularly a kind of wrapping paper Cypres and its system
Preparation Method.
Background technology
Cypres are a kind of sheet surface treating agents, and it is typically coated on paper surface by carrier of starch, with
Paper water-resistance is improved, and improves paper strength and paper surface properties, and then obtains the paper with high surface property
.And in field of papermaking, based on considering in terms of resource, the energy, environment, modern paper industry is main
Tend to paper pulp raw material chopped fiber, waste paper secondary stock usury be continuously increased with, amount of filler, paper lightweight,
The directions such as paper machine production high speed, papermaking alkalization, white-water system closure are developed, the change of these Papermaking Conditions
So that papermaking environments are harsher, so renewal is proposed to the development and application of related papermaking chemical product, it is higher
It is required that.For package paper, in order to obtain light basis weight, high intensity, high water resistant, high surface property
Package paper, its top sizing processing is particularly important, and the selection of particularly Cypres is of crucial importance.
At present, the conventional commodity-type Cypres of in the market be mainly the styrene of various converted starches and synthesis-
Acrylate polymer emulsion.Wherein, styrene-acrylate polymer type of latex type Cypres synthesis technique
Simple and environmentally-friendly, strong adaptability, and can assign paper a variety of excellent properties, the production of various sheet paper products can be met
Demand.Therefore, in the production process of wrapping paper, the use of polymer emulsion Cypres is increasingly by weight
Depending on to expect under relatively low Cypres consumption with regard to the wrapping paper of high waterproof energy can be obtained.Meanwhile, in reality
Using when, packaging paper product also there is moisture absorption phenomenon, humidity is bigger, and wrapping paper moisture absorption phenomenon is more serious.The opposing party
Face, as Papermaking Conditions are further harsh, especially a large amount of of secondary fiber papermaking raw material use, general polymer
Cypres can not meet production and the use requirement of wrapping paper.Therefore, a kind of water repelling property and protection against the tide are researched and developed
The good efficient wrapping paper of performance is very necessary with Cypres.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of water-resistance for the shortcoming that overcomes above-mentioned prior art to exist
Energy and the good Cypres of humidity resistance.
Therefore, the technical solution adopted by the present invention is as follows：A kind of wrapping paper Cypres, it is by following each group
It is grouped into, the parts by weight of each component are：
Natural polymer：30~70,
Natural macromolecule modification agent：0.2~1.0,
Unsaturated hard monomer：6~30,
Unsaturated soft monomer：6~20,
Modified petroleum resin：6~40,
Cationic monomer：1~3,
Function monomer：0.5~3,
Initiator I：0.5~3,
Initiator II：0.5~3,
Deionized water, consumption is the final solid content for ensureing Cypres 25~30%；
Described modified petroleum resin is made up of following each component, and the parts by weight of each component are：
Petropols：85~95,
Maleic anhydride：5~15,
Polymerization inhibitor：0.5~2.5,
Described Petropols are the through-stone oleoresin of carbon nine；
Described polymerization inhibitor is MEHQ, hydroquinones, o-sec-butyl 4,6- dinitrophenol, to benzene
One kind in quinone, methylnaphthohydroquinone, 2- TBHQs, 2,5- di-tert-butyl hydroquinones；
Described natural polymer is one or both of cation cassava starch, cationic maize starch
The mixture of arbitrary proportion；Compared with low molecular weight emulsifier, natural polymer is used in emulsion polymerization
As emulsifying agent or dispersant, the storage stability of emulsion can be significantly improved；In addition, cationic starch simultaneously can
Grafting site is provided as reaction raw materials, graft copolymerization is carried out with unsaturated ethylene alkenyl monomer；
Described natural macromolecule modification agent is the mixed of one or both of alpha-amylase, beta amylase arbitrary proportion
Compound；Catalyzing hydrolysis is carried out to cation cassava starch, cationic maize starch using natural macromolecule modification agent enzyme,
To obtain the starch with certain palliating degradation degree, and improve the reactivity of starch molecule；Enzymatic hydrolysis starch is
A kind of important starch conversion method, compared with general catalyst, enzyme has high catalytic efficiency；
Described unsaturated hard monomer is styrene, α-methylstyrene, methyl methacrylate, vinylacetate
In one or more arbitrary proportions mixture；
Described unsaturated soft monomer is ethyl acrylate, butyl acrylate, Hexyl 2-propenoate, Isooctyl acrylate monomer
In one or more arbitrary proportions mixture；
Described cationic monomer is acrylyl oxy-ethyl-trimethyl salmiac, methylacryoyloxyethyl trimethyl chlorine
Change ammonium, acryloxyethyldimethyl benzyl ammonium chloride, diallyldimethylammonium chloride, dimethylaminoethyl acrylate methyl
The mixture of one or more arbitrary proportions in base amino ethyl ester；
Described function monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, NMA, metering system
The mixture of one or more arbitrary proportions in acid glycidyl ester, acrylic acid, methacrylic acid；
Described initiator I is one kind in hydrogen peroxide, potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate；Trigger
Agent I is used for triggering unsaturated ethylene alkenyl monomer, the natural polymer of modification, the free radical of modified C 9 petroleum resin
Polymerization；
Described initiator II is in TBHP, benzoyl hydroperoxide, peroxide -2-ethyl hexanoic acid tert-butyl
One or more arbitrary proportions mixture；Initiator II is used for further improving monomer conversion, reduction residual
Content of monomer.
Further, described wrapping paper also includes the pH adjusting agent of 0.2~4 parts by weight with Cypres.
Further, described pH adjusting agent be formic acid, glacial acetic acid, mass concentration be 10% watery hydrochloric acid, quality
Concentration is one kind in 10% dilute sulfuric acid.
The preparation method of above-mentioned wrapping paper Cypres, its following steps are carried out：
1) preparation of modified petroleum resin
Petropols, maleic anhydride and polymerization inhibitor are added in the reactor, and rise temperature is to 220~250 DEG C, stirring
4~6h of lower insulation reaction, produces modified petroleum resin；
2) preparation of Cypres
1) monomer solution is prepared：By unsaturated hard monomer, unsaturated soft monomer, above-mentioned steps 1) modification for preparing
Petropols, cationic monomer and function monomer are well mixed, obtain monomer solution；
2) initiator I solution is prepared：By the well mixed obtained initiator I of initiator I and 15% deionized water
Solution；
3) preparation of Cypres：Natural polymer is added in agitator, the reactor of thermometer
Compound, natural macromolecule modification agent and 85% deionized water, are heated to 70~90 DEG C, are incubated under agitation
React 0.5~2h；Then pH adjusting agent is added into reactor, and by reaction temperature regulation and control to 75~85 DEG C；
During monomer solution and initiator I solution are added drop-wise into reaction vessel simultaneously from both sides respectively at 75~85 DEG C, during dropwise addition
Between be 2~3h, and ensure the two drip simultaneously, after dripping, continuation at 75~85 DEG C 1~2h of insulation reaction；
Initiator II is added in reactor afterwards, continues 1.5~3h of insulation reaction at 75~85 DEG C；Cooling, cooling,
Discharging produces the Cypres that solid content is 25~30%.
In the preparation process of the present invention, the radical copolymerization of unsaturated monomer and its and natural polymer
Graft copolymerization, radical copolymerization and its emulsification in emulsion of modified C 9 petroleum resin and unsaturated monomer
Several reactions such as scattered are carried out simultaneously, and what is obtained is that natural polymer-polyacrylate-modification C 9 petroleum resin is total to
Copolymer emulsion, while unreacted modified C 9 petroleum resin is also emulsified and is dispersed in copolymer emulsion.Carbon nine is
Petropols are the low pole materials being polymerized by styrene, methyl styrene, indenes etc., with excellent water resistant,
Anti-aging, resistance to acids and bases, during as paper surface sizing agent, shows good water repelling property and humidity resistance；
Moreover, after maleic anhydride modified, the polarity acid anhydrides that can be combined with paper fiber is introduced on C 9 petroleum resin molecule
Group, hence it is evident that improve Petropols keeping on paper and adsorb.In addition, in the preparation process of the present invention,
Appropriate cation group is incorporated on copolymer molecule chain, emulsion intercalation method is added, copolymer is improved
Keeping on paper and adsorb, improve the anti-foreign ion interference performance of emulsion.
Just because of above-mentioned advantage, the applying glue of Cypres prepared by the present invention in low resin added or rather harsh
The sizing efficiency having had under environment, it is also excellent with curing fast, cost performance height, the good, safety and environmental protection of humidity resistance etc.
Point.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
(1) preparation of modified C 9 petroleum resin
85 parts of C 9 petroleum resins, 15 parts of maleic anhydrides, 0.5 part of MEHQ are added in the reactor,
Temperature is raised to 220 DEG C, the lower insulation reaction 5h of stirring produces modified C 9 petroleum resin.
(2) preparation of Cypres
1) monomer solution is prepared：By 30 parts of styrene, 10 parts of butyl acrylates, 10 parts of ethyl acrylates, 20
The modification C 9 petroleum resin of part above-mentioned steps (1) preparation, 3 parts of dimethylaminoethyl methacrylates mixing are equal
It is even, obtain monomer solution；
2) initiator I solution is prepared：By 3 parts of hydrogen peroxide, the well mixed obtained initiator of 35 parts of deionized waters
I solution；
3) preparation of surface sizing agent emulsion：In with agitator, the reactor of thermometer add 30 parts of sun from
Sub- tapioca, 0.3 part of alpha-amylase, 198 parts of deionized waters, are heated to 70 DEG C, are incubated under agitation
React 2h；Then 4 parts of formic acid are added into reactor, and by reaction temperature regulation and control to 75 DEG C；Will at 75 DEG C
During monomer solution and initiator I solution are added drop-wise to reaction vessel simultaneously from both sides respectively, time for adding is 2h, and is protected
The two is dripped card simultaneously, after dripping, and continues the insulation reaction 2h at 75 DEG C；Afterwards by 1.5 parts of tert-butyl group mistakes
Hydrogen oxide is added in reactor, continues the insulation reaction 2h at 75 DEG C；Cooling, cooling, discharging are produced containing solid
Measure the wrapping paper Cypres for 30%.
Embodiment 2
(1) preparation of modified C 9 petroleum resin
88 parts of C 9 petroleum resins, 12 parts of maleic anhydrides, 2 parts of hydroquinones, rise temperature are added in the reactor
Degree is to 230 DEG C, and the lower insulation reaction 5.5h of stirring produces modified C 9 petroleum resin.
(2) preparation of Cypres
1) monomer solution is prepared：By 5 parts of α-methylstyrenes, 15 parts of methyl methacrylates, 15 parts of acrylic acid
Modification C 9 petroleum resin, 1 part of methylacryoyloxyethyl front three prepared by own ester, 10 parts of above-mentioned steps (1)
Ammonium chloride, 2.5 parts of hydroxy-ethyl acrylates, 0.5 part of methacrylic acid are well mixed, and obtain monomer solution；
2) initiator I solution is prepared：0.6 part of potassium peroxydisulfate, well mixed be made of 45 parts of deionized waters are triggered
Agent I solution；
3) preparation of surface sizing agent emulsion：In with agitator, the reactor of thermometer add 30 parts of sun from
Ziyu rice starch, 0.5 part of beta amylase, 254 parts of deionized waters, are heated to 75 DEG C, are incubated under agitation
React 1.5h；Then 3 parts of glacial acetic acid are added into reactor, and by reaction temperature regulation and control to 80 DEG C；At 80 DEG C
Lower that monomer solution and initiator I solution are added drop-wise into reaction vessel simultaneously from both sides respectively, time for adding is 2.5h,
And ensure that the two is dripped simultaneously, after dripping, continue the insulation reaction 2h at 80 DEG C；Afterwards by 0.6 part of peroxide
Benzoic acid is added in reactor, continues the insulation reaction 1.5h at 80 DEG C；Cooling, cooling, discharging are produced containing solid
Measure the wrapping paper Cypres for 30%.
Embodiment 3
(1) preparation of modified petroleum resin
90 parts of C 9 petroleum resins, 10 parts of maleic anhydrides, 1.5 parts of o-sec-butyls 4,6- bis- are added in the reactor
Nitrophenol, rise temperature is to 240 DEG C, and the lower insulation reaction 4.5h of stirring produces modified C 9 petroleum resin.
(2) preparation process of Cypres：
1) monomer solution is prepared：By 9 parts of styrene, 6 parts of vinylacetates, 16 parts of ethyl acrylates, 4 part third
Modification C 9 petroleum resin, 1.5 parts of acrylyl oxy-ethyls three prepared by the different monooctyl ester of olefin(e) acid, 35 parts of above-mentioned steps (1)
Ammonio methacrylate, 0.5 part of NMA are well mixed, and obtain monomer solution；
2) initiator I solution is prepared：By 1 part of ammonium persulfate, the well mixed obtained initiator of 40 parts of deionized waters
I solution；
3) preparation of surface sizing agent emulsion：In with agitator, the reactor of thermometer add 30 parts of sun from
Sub- tapioca, 20 parts of cationic maize starch, 0.3 part of alpha-amylase, 0.3 part of beta amylase, 226 parts go from
Sub- water, is heated to 80 DEG C, under agitation insulation reaction 1h；Then 0.4 part 10% is added into reactor
Watery hydrochloric acid, and by reaction temperature regulation and control to 85 DEG C；At 85 DEG C by monomer solution and initiator I solution respectively from
Both sides are added drop-wise in reaction vessel simultaneously, and time for adding is 3h, and ensure that the two is dripped simultaneously, after dripping,
Continue the insulation reaction 1.5h at 85 DEG C；Afterwards by 2 parts of TBHPs, 1 part of peroxidating (2- ethyl hexyl
Acid) tert-butyl ester is added in reactor, continues the insulation reaction 2.5h at 85 DEG C；Cooling, cooling, discharging are produced
Solid content is 25% wrapping paper Cypres.
Embodiment 4
(1) preparation of modified C 9 petroleum resin
92 parts of C 9 petroleum resins, 8 parts of maleic anhydrides, 1.5 parts of 1,4-benzoquinone are added in reactor, temperature is raised
To 235 DEG C, the lower insulation reaction 6h of stirring produces modified C 9 petroleum resin.
(2) preparation of Cypres
1) monomer solution is prepared：By 2 parts of vinylacetates, 6 parts of methyl methacrylates, 12 parts of acrylic acid second
Modification C 9 petroleum resin prepared by ester, 40 parts of above-mentioned steps (1), 2 parts of dimethylamine second
Ester, 1 part of acryloxyethyldimethyl benzyl ammonium chloride, 0.8 part of hydroxypropyl acrylate, 0.2 part of methacrylic acid
It is well mixed, obtain monomer solution；
2) initiator I solution is prepared：1.5 parts of sodium peroxydisulfates, well mixed be made of 57 parts of deionized waters are triggered
Agent I solution；
3) preparation of surface sizing agent emulsion：In with agitator, the reactor of thermometer add 60 parts of sun from
Ziyu rice starch, 0.2 part of alpha-amylase, 0.6 part of beta amylase, 321 parts of deionized waters, are heated to 85 DEG C,
Insulation reaction 45min under agitation；Then 1.5 part of 10% dilute sulfuric acid is added into reactor, and by reaction temperature
Regulate and control to 75 DEG C；Monomer solution and initiator I solution are added drop-wise into reaction simultaneously from both sides respectively at 75 DEG C to hold
In device, time for adding is 2.5h, and ensures that the two is dripped simultaneously, after dripping, and continues to be incubated instead at 75 DEG C
Answer 1h；2 parts of TBHPs, 1 part of benzoyl hydroperoxide are added in reactor afterwards, continued at 75 DEG C
Lower insulation reaction 2h；Cooling, cooling, discharging produce the wrapping paper Cypres that solid content is 25%.
Embodiment 5
(1) preparation of modified C 9 petroleum resin
95 parts of C 9 petroleum resins, 5 parts of maleic anhydrides, 2.5 parts of methylnaphthohydroquinones, rise temperature are added in the reactor
Degree is to 245 DEG C, and the lower insulation reaction 4h of stirring produces modified C 9 petroleum resin.
(2) preparation of Cypres
1) monomer solution is prepared：By 25 parts of vinylacetates, 8 parts of butyl acrylates, 2 parts of Hexyl 2-propenoates,
Modification C 9 petroleum resin prepared by 25 parts of above-mentioned (1) steps, 1.5 parts of dimethylaminoethyl methacrylates,
1 part of diallyldimethylammonium chloride, 2 parts of GMAs are well mixed, and obtain monomer solution；
2) initiator I solution is prepared：2.5 parts of hydrogen peroxide, well mixed be made of 61 parts of deionized waters are triggered
Agent I solution；
3) preparation of surface sizing agent emulsion：In with agitator, the reactor of thermometer add 70 parts of sun from
Sub- tapioca, 0.7 part of alpha-amylase, 0.3 part of beta amylase, 343 parts of deionized waters, are heated to 90 DEG C,
Insulation reaction 0.5h under agitation；Then 3.5 parts of formic acid are added into reactor, and by reaction temperature regulation and control to 80 DEG C；
During monomer solution and initiator I solution are added drop-wise into reaction vessel simultaneously from both sides respectively at 80 DEG C, time for adding
For 2h, and ensure that the two is dripped simultaneously, after dripping, continuation insulation reaction 1h at 80 DEG C；Afterwards by 1
Part TBHP, 1.5 parts of peroxidating (2 ethyl hexanoic acid) tert-butyl esters are added in reactor, continue to exist
Insulation reaction 3h at 80 DEG C；Cooling, cooling, discharging produce the wrapping paper Cypres that solid content is 25%.
Embodiment 6
(1) preparation process of modified C 9 petroleum resin：
90 parts of C 9 petroleum resins, 10 parts of maleic anhydrides, 1.2 parts of 2- tert-butyl groups are added in reactor to benzene two
Phenol, rise temperature is to 250 DEG C, and the lower insulation reaction 5h of stirring produces modified C 9 petroleum resin.
(2) preparation process of Cypres：
1) monomer solution is prepared：18 parts of methyl methacrylates, 4 parts of butyl acrylates, 2 parts of acrylic acid are different
Modification C 9 petroleum resin, 2 parts of methylacryoyloxyethyl front threes prepared by monooctyl ester, 30 parts of above-mentioned (1) steps
Ammonium chloride, 1.5 parts of methacrylic acids are well mixed, and obtain monomer solution；
2) initiator I solution is prepared：By 2 parts of ammonium persulfates, the well mixed obtained initiator of 37 parts of deionized waters
I solution；
3) preparation of surface sizing agent emulsion：In with agitator, the reactor of thermometer add 15 parts of sun from
Sub- tapioca, 30 parts of cationic maize starch, 0.7 part of beta amylase, 211 parts of deionized waters, heat temperature raising
To 85 DEG C, insulation reaction 1.5h under agitation；Then 2 parts of glacial acetic acid are added into reactor；Will at 85 DEG C
During monomer solution and initiator I solution are added drop-wise to reaction vessel simultaneously from both sides respectively, time for adding is 3h, and is protected
The two is dripped card simultaneously, after dripping, and continues the insulation reaction 1.5h at 85 DEG C；Afterwards by 1 part of peroxide benzene first
Acid, 1 part of peroxidating (2 ethyl hexanoic acid) tert-butyl ester are added in reactor, continue the insulation reaction 1.5h at 85 DEG C；
Cooling, cooling, discharging produce the Novel packaging paper Cypres that solid content is 30%.
Application effect
The sizing efficiency of Cypres prepared by each embodiment is shown in Table 1.
The sizing efficiency of Cypres prepared by each embodiment of table 1
Note：Bodystock paper is 110g/m2Fluting medium；Coating fluid starch concentration is 8%；The addition of aluminum sulfate is the percentage for accounting for coating fluid.
Claims (4)
1. a kind of wrapping paper Cypres, it is made up of following each component, and the parts by weight of each component are：
Deionized water, consumption is the final solid content for ensureing Cypres 25~30%；
Described modified petroleum resin is made up of following each component, and the parts by weight of each component are：
Petropols：85~95,
Maleic anhydride：5~15,
Polymerization inhibitor：0.5~2.5,
Described Petropols are the through-stone oleoresin of carbon nine,
Described polymerization inhibitor is MEHQ, hydroquinones, o-sec-butyl 4,6- dinitrophenol, to benzene
One kind in quinone, methylnaphthohydroquinone, 2- TBHQs, 2,5- di-tert-butyl hydroquinones；
Described natural polymer is one or both of cation cassava starch, cationic maize starch
The mixture of arbitrary proportion；
Described natural macromolecule modification agent is the mixed of one or both of alpha-amylase, beta amylase arbitrary proportion
Compound；
Described unsaturated hard monomer is styrene, α-methylstyrene, methyl methacrylate, vinylacetate
In one or more arbitrary proportions mixture；
Described unsaturated soft monomer is ethyl acrylate, butyl acrylate, Hexyl 2-propenoate, Isooctyl acrylate monomer
In one or more arbitrary proportions mixture；
Described cationic monomer is acrylyl oxy-ethyl-trimethyl salmiac, methylacryoyloxyethyl trimethyl chlorine
Change ammonium, acryloxyethyldimethyl benzyl ammonium chloride, diallyldimethylammonium chloride, dimethylaminoethyl acrylate methyl
The mixture of one or more arbitrary proportions in base amino ethyl ester；
Described function monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, NMA, metering system
The mixture of one or more arbitrary proportions in acid glycidyl ester, acrylic acid, methacrylic acid；
Described initiator I is one kind in hydrogen peroxide, potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate；
Described initiator II is in TBHP, benzoyl hydroperoxide, peroxide -2-ethyl hexanoic acid tert-butyl
One or more arbitrary proportions mixture.
2. wrapping paper Cypres according to claim 1, it is characterised in that it also includes 0.2~4 weight
The pH adjusting agent of part.
3. wrapping paper Cypres according to claim 2, it is characterised in that described pH adjusting agent is
One kind in the dilute sulfuric acid that watery hydrochloric acid that formic acid, glacial acetic acid, mass concentration are 10%, mass concentration are 10%.
4. the preparation method of any one of the claim 1-3 wrapping paper Cypres, its following steps are carried out：
1) preparation of modified petroleum resin
Petropols, maleic anhydride and polymerization inhibitor are added in the reactor, and rise temperature is to 220~250 DEG C, stirring
4~6h of lower insulation reaction, produces modified petroleum resin；
2) preparation of Cypres
1) monomer solution is prepared：By unsaturated hard monomer, unsaturated soft monomer, above-mentioned steps 1) modification for preparing
Petropols, cationic monomer and function monomer are well mixed, obtain monomer solution；
2) initiator I solution is prepared：By the well mixed obtained initiator I of initiator I and 15% deionized water
Solution；
3) preparation of Cypres：Natural polymer is added in agitator, the reactor of thermometer
Compound, natural macromolecule modification agent and 85% deionized water, are heated to 70~90 DEG C, are incubated under agitation
React 0.5~2h；Then pH adjusting agent is added into reactor, and by reaction temperature regulation and control to 75~85 DEG C；
During monomer solution and initiator I solution are added drop-wise into reaction vessel simultaneously from both sides respectively at 75~85 DEG C, during dropwise addition
Between be 2~3h, and ensure the two drip simultaneously, after dripping, continuation at 75~85 DEG C 1~2h of insulation reaction；
Initiator II is added in reactor afterwards, continues 1.5~3h of insulation reaction at 75~85 DEG C；Cooling, cooling,
Discharging produces the Cypres that solid content is 25~30%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101403204A (en) * | 2008-10-07 | 2009-04-08 | 杭州杭化播磨造纸化学品有限公司 | Surface sizing agent for amphiprotic papermaking and its preparation method |
| CN101649579A (en) * | 2009-09-01 | 2010-02-17 | 陕西科技大学 | Method for preparing cation high molecular base petroleum resin neutral sizing agent |
| CN102127191A (en) * | 2010-12-24 | 2011-07-20 | 江苏富淼科技股份有限公司 | Preparation method of graft copolymer for surface sizing |
| CN102140768A (en) * | 2010-12-20 | 2011-08-03 | 杭州杭化播磨造纸化学品有限公司 | Novel cationic surface sizing agent and preparation method thereof |
| WO2012069460A1 (en) * | 2010-11-25 | 2012-05-31 | Basf Se | Finely divided, cationic or amphoteric, aqueous polymer dispersions, process for their preparation, their use, cationic or amphoteric protective colloids and their preparation |
| CN102995488A (en) * | 2012-12-05 | 2013-03-27 | 陕西科技大学 | Method for preparing cationic rosin/C9 petroleum resin sizing agent |
-
2016
- 2016-04-27 CN CN201610277785.6A patent/CN107313292A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101403204A (en) * | 2008-10-07 | 2009-04-08 | 杭州杭化播磨造纸化学品有限公司 | Surface sizing agent for amphiprotic papermaking and its preparation method |
| CN101649579A (en) * | 2009-09-01 | 2010-02-17 | 陕西科技大学 | Method for preparing cation high molecular base petroleum resin neutral sizing agent |
| WO2012069460A1 (en) * | 2010-11-25 | 2012-05-31 | Basf Se | Finely divided, cationic or amphoteric, aqueous polymer dispersions, process for their preparation, their use, cationic or amphoteric protective colloids and their preparation |
| CN102140768A (en) * | 2010-12-20 | 2011-08-03 | 杭州杭化播磨造纸化学品有限公司 | Novel cationic surface sizing agent and preparation method thereof |
| CN102127191A (en) * | 2010-12-24 | 2011-07-20 | 江苏富淼科技股份有限公司 | Preparation method of graft copolymer for surface sizing |
| CN102995488A (en) * | 2012-12-05 | 2013-03-27 | 陕西科技大学 | Method for preparing cationic rosin/C9 petroleum resin sizing agent |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108004841B (en) * | 2017-12-25 | 2020-10-20 | 浙江传化华洋化工有限公司 | Surface sizing agent and preparation method thereof |
| CN108004841A (en) * | 2017-12-25 | 2018-05-08 | 浙江传化华洋化工有限公司 | A kind of Cypres and preparation method thereof |
| CN108708222A (en) * | 2018-04-23 | 2018-10-26 | 句容市兴武包装有限公司 | A kind of preparation method of Mixidene |
| CN108677606A (en) * | 2018-06-07 | 2018-10-19 | 华东理工大学 | A kind of preparation method of epoxy type wet strength agent |
| CN109137609A (en) * | 2018-07-20 | 2019-01-04 | 蚌埠市奥特纸箱机械有限公司 | A method of improving corrugated paper ring Asia intensity |
| CN109337012B (en) * | 2018-08-31 | 2021-07-09 | 恒河材料科技股份有限公司 | Preparation method of phenol modified copolymerized petroleum resin |
| CN109337012A (en) * | 2018-08-31 | 2019-02-15 | 恒河材料科技股份有限公司 | A kind of preparation method of phenol modified copolymer Petropols |
| CN110894256A (en) * | 2018-09-12 | 2020-03-20 | 上海昶法新材料有限公司 | Styrene derivative copolymer sizing agent and preparation method thereof |
| CN110894256B (en) * | 2018-09-12 | 2022-03-18 | 上海昶法新材料有限公司 | Styrene derivative copolymer sizing agent and preparation method thereof |
| CN112236557A (en) * | 2018-09-18 | 2021-01-15 | 栗田工业株式会社 | Surface sizing agent for papermaking |
| CN112236557B (en) * | 2018-09-18 | 2021-10-15 | 栗田工业株式会社 | Surface sizing agent for papermaking |
| US11603630B2 (en) | 2018-09-18 | 2023-03-14 | Kurita Water Industries Ltd. | Surface sizing agent for papermaking |
| CN110407969A (en) * | 2019-07-18 | 2019-11-05 | 广东诚铭化工科技有限公司 | A kind of high-efficiency surface sizing agent and its preparation method and application |
| CN114163562A (en) * | 2021-12-24 | 2022-03-11 | 宁波市嘉化新材料科技有限公司 | A kind of anti-moisture permeation agent for paper and preparation method thereof |
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Application publication date: 20171103 |